Ester ether-acetal copolymers and process of preparing same



United States Patent 3,378,527 ESTER ETHER-ACETAL COPOLYMERS AND PROCESSOF PREPARING SAME Leslie C. Case and Laura K. Case, both of 14 LoclrlandRoad, Winchester, Mass. 01890 No Drawing. Continuation-impart ofapplication Ser. No. 168,062, Jan. 23, 1962. This application Sept. 8,1966, Ser. No. 578,425

62 Claims. (Cl. 260-67) ABSTRACT OF THE DISCLOSURE Ternary copolymerscontaining ester, ether, and aectal units and having chemically reactivehydroxyl or carboxyl chain-end groups are described. Two general typesof ternary copolymers are provided, one containing the ester, ether, andacetal units in random sequences, the other containing polyacetal blocksterminated and/or linked together by ester-ether copolymer segments. Thefirst type of terpolyrner is prepared by reacting together an aldehyde,a cyclic anhydride of an organic dicarboxylic acid and an epoxide oroxetane, and, preferably, a starter with active hydrogen-containingradicals. The second type of terpolymer is prepared by employing ahydroxyl-terminated polyacetal as the starter.

This application is a continuation-impart of applications Ser. No.168,062, filed Jan. 23, 1962, now abandoned, Ser. No. 212,466, filedJuly 25, 1962, now abandoned, and Ser. No. 456,816, filed May 18, 1965.

This invention is concerned wit-h novel polymeric compositions and theirproduction. More particularly, this invention is concerned with novelternary copolymers related to the classes broadly referred to ascondensation and addition polymers, and having ester, ether, and acetallinkages in substantial proportion, and with the novel processes ofproducing such materials.

It is a principal object of the present invention to provide novelhydroxylor carboxyl-terminated ternary copolymeric compositions havingmain polymer chains composed of a multiplicity of ester, ether, andacetal members, and to provide a novel process for producing suchcompositions starting with readily available low-priced monomers. Theternary compositions provided may be random copolymers in which thesemembers are distributed substantially randomly within the polymerchains, or they may be ordered, so-called block copolymers, in whichblocks or segments of recurring acetal members derived from a preformedpolyacetal block alternate with blocks of a random binarypolyester-ether copolymer. It is a further object to provide suchcompositions over a wide range of molecular weights in a fusible,soluble thermoplastic form, or in a cross-linked thermosetting form. Itis a still further object to provide compositions which may bemonofunctional or polyfunctional, that is, the polymer chains may carryone or several functional groups capable of entering into constructivechemical reaction, if desired.

It is yet another object of this invention to prepare conveniently andeconomically fire-resistant polymers of the above type. A still furtherobject of this invention is to provide unsaturated copolymers withimproved color.

It has been found that aldehydes will react with cyclic ethers selectedfrom the group consisting of epoxides and oxethanes, and organicpolycarboxylic acid anhydrides to form ternary copolymers. It hasfurther been discovered that the polymerization is greatly improved andthat more desirable compositions are obtained if a polymerizationstarter having an active-hydrogen-containing radical is employed.Anhydrides which are much preferred for use are "ice cyclic anhydride ofpolycarboxylic acids, and particularly cyclic anhydrides of dicarboxylicacids. Linear polyanhy- 'drides of dicarboxylic acids may be employedbut are less reactive and lead to undesirable broadening of the polymermolecular weight distribution.

In accord with the present invention novel polymeric products areproduced by reacting together (1) a cyclic ether selected from the groupconsisting of epoxides and oxetanes, (2) a cyclic anhydride of anorganic polycarboxylic acid, and (3) an aldehyde, at a temperature ofabout 70 C. to about 225 C. sufiicient for the reactants to polymerizeand at a pressure at least equal to the vapor pressure of the system atthe reaction temperature.

According to the preferred embodiment of the invention, the preferredpolymeric compositions are produced by reacting together (1) a cyclicether selected from the group consisting of epoxides and oxetanes, (2) acyclic anhydride of an organic polycarboxylic acid, (3) an aldehyde, and(4) a polymerization starter of the group consisting of water, inorganicacids capable of eifectin-g a ring-opening reaction of cyclic ethers,and organic compounds with active-hydrogen-containing radicals selectedfrom the group consisting of hydroxyl, carboxyl, sulfhydryl, and aminoradicals at a temperature of about 70 C. to about 225 C. sufiicient forthe reactants to polymerize, and at a pressure at least equal to thevapor pressure of the system at the reaction temperature.

If only difunctionally reactive cyclic monoethers, cyclic monoanhydridesand monoaldehydes are employed with or without the above describedpolymerization starters, non-cross-linked, fusible, soluble,thermoplastic random copolymers which are linear or branched withsubstantially linear main polymer chains are obtained. Each polymermolecule is mono-, di-, or higher polyfunctional and has terminalcarboxylic acid groups or hydroxyl groups. If multifunctional reactants,such as diepoxides, triepoxides, or higher polyepoxides, ordianhydrides, or dialdehydes, are coreacted with monoethers,monoanhydrides, and monoaldehydes, in the absence or presence of apolymerization starter, the resulting copolymers will be more highlybranched, and if a suflicient proportion of these multifunctionalreactants is employed, a crosslinked, infusible, insoluble compositionresults.

The ternary copolymers resulting from the process of this invention areproduced by an addition mechanism, but have the formal structure andcharacteristics of condensation polymers. Polymerization by the aboveprocess proceeds by random stepwise addition and the polymeric productshave ester, ether, and acetal units interspersed more or less at randomalong the polymer chains. The number of the various units in the ternarycopolymers is distributed more or less according to a Poissondistribution, such as:

Where:

X= (OR) is a 1,3- or 1,4-oxyalkylene radical derived from a cyclic etherby a ring-opening reaction, and R is a 1,2-alkylene or 1,3-a1kyleneradical is a residue derived from a cyclic anhydride by a ringopeningreaction, and R is a hydrocarbon radical connecting two carboxylic acidcarbonyl functions Z=(O-OH) is an acetal unit and R" is a radicalattached to the carbon atom of the aldehyde group.

The most interesting compounds are those in which R is a lower alkylenesuch as 1,2-ethylene, 1,2-propylene and 1,2-butylene; R is1,2-phenylene, a lower alkylene and especially ethylene, a lower alkeneand particularly ethenylene (CH=CH-), and the hexachlorobicyeloheptylenegroup, and R" is hydrogen, methyl and trihalomethyl.

The polymeric compositions provided herewith are broadly described asrandom polyester-ether-acetal copolymers since they contain amultiplicity of ester, ether, and acetal linkages distributed in arandom fashion within the polymer chain. The term random is used todifferentiate these polymers from so-called block polymers or polymerswith a repeating sequence of identical structural segments in thepolymer chain. While the overall structure of the ternary copolymers ofthe present invention can best be described as random it should be notedthat the sequences of the individual respective linkages in the polymerchain are not precisely random in that only certain sequences oflinkages may be present. As a polymer chain is traversed certainlimitations apply to the sequential order in which the linkages appear.Specifically, it will be understood by those skilled in the art that theester linkages always are present in pairs, separated by the hydrocarbonradical which connected the carboxylic carbonyl groups of the originalanhydride, and

such a pair of ester linkages is usually separated by one or more etheror acetal units from a second pair of ester linkages derived fromanother anhydride molecule. The ether linkages may occur either singlyor in runs with the length of each run containing from two to aboutfifteen cyclic ether units in the main chain and frequently being asmuch as three or four, rarely being as much as 8 or 10, and very rarelyexceeding fifteen. Thus the polymer chain will contain polyethersegments composed of a mixture of monooxyalkylene, dioxyalkylene,trioxyalkylene, and higher polyoxyalkylene units. The acetal members mayalso occur singly or in runs with the acetal units in each run rangingfrom two to about 25, and more commonly from two to about fifteen, andfrequency from about two to ten. An acetal unit or segment may beadjacent to either an ether or an ester unit.

If the reactants with the exception of the polymerization starter aredifunctionally reactive only, that is, if the ternary copolymers areprepared by reacting together (1) a cyclic monoanhydride of an organicpolycarboxylic acid, (2) a cyclic monoether selected from the groupconsisting of monoepoxides and monooxetanes, and (3) a monoaldehyde,with a polymerization starter as described herein-above, thermoplasticfusible, soluble, random ternary copolymers are produced which consistof linear main polymer chains composed of polyoxyalkylene segments ofthe general formula (--OR--) anhydride residues of the formula OC-R'C llII 0 and acetal segments of the formula (OHO)m wherein R, R, and R havethe above assigned meaning, and m and n are positive whole numbersvarying from one to about fifteen, with the average value ranging fromabout 1.25, to not more than eight, and generally not more than six andfrequently not more than four, said polymer chains originating at oneend in a branch-like or tentacular fashion from, and being attachedthrough ester or ether linkages to, the polymerization starter residuewhich provides a central core, and with said chains being terminated atthe other end by a hydroxyl or carboxylic acid end group. Thefunctionality of the polymer, that is, the number of hydroxyl orcarboxyl end groups per polymer molecule, will be equal to thefunctionality of the polymerization starter under these conditions. Apolymerization starter with only one active-hydrogen-containing groupwill give rise to a polymer molecule composed of a single polymer chainterminated by a hydroxyl or carboxyl group; a difunctional starter, suchas a glycol, for example, will produce compositions composed of polymermolecules having two polymer chains emanating from the starter residuewith each chain having either a hydroxyl or a carboxyl end group, .andwith a trifunctional starter, such as glycerol, for example, the ternarycopolymer will consist of polymer molecules having three hydroxylorcarboxyl-terminated polymer chains attached to the starter. Thefunctionality of the polymer is thus determined by the functionality ofthe starter employed in combination with the monoepoxide, themonoanhydride and the monoaldehyde.

Such random thermoplastic terpolymers produced from cyclic monoethers,cyclic monoanhydrides, monoaldehydes and a polymerization starter may berepresented by the general structural formula:

wherein R, R and R have the above-assigned meaning, P is the residue ofa polymerization starter of functionality f, n is an integer varyingfrom zero to about ten, and preferably from zero to about five, andhaving an average value of from about 1.25 to about 6, m is an integervarying from zero to about fifteen with the average value of m rangingfrom about 1.25 to eight, and with the sum of it plus in between esterlinkages being at least 1.0, p is an integer equal to or larger than oneand p is an integer equal to or larger than zero, q is an integervarying from zero to about fifty, with an average value of at leastabout one.

Desirable copolymers will contain from at least 0.1 to not more than 50percent and more commonly from about one to about 25 percent by weightof residues derived from the polymerization starter and from about oneto about 75 percent and preferably from about 5 to 50 percent by weightof acetal units with the remainder of the weight being composed ofcyclic ether residues and anhydride residues in a proportion such thatthe molar ratio R to R will range from about 1.5, and preferably fromabout 2, to not more than ten, and preferably to less than six.Cross-linked ternary compositions will generally contain from about 0.1to 25 percent by weight of starter residues and from about 5 to 50percent by weight or" acetal units with the remainder of the Weightbeing cyclic ether residues and anhydride residues in a molar ratio ofR/R' from about 1.5 to about 6, and with at least 2 percent, and usuallyat least five percent by Weight of the total composition being derivedfrom polyfunctional monomers with a functionality of at least four.

The cyclic ethers which can be used in this invention comprise1,2-alkylene oxides, also known as epoxides or oxiranes, and1,3-alkylene oxides, also known as oxetanes. The cyclic ethers may carrysubstituents which do not interfere with the polymerization, such as,for example, alkyl, alkylene, alkoxy, carbalkoxy, halogen radicals, andthe like. Particularly suitable cyclic ethers are those having from twoto twenty carbon atoms and from zero to 3 halogen atoms such as chloroor bromo radicals. Especially preferred for use in the present inventionare the saturated aliphatic terminal 1,2-monoepoxides having from 2 tonot more than ten, and advisably not more than six carbon atoms, andhaving the general structural formula wherein the residual valence maybe satisfied by hydrogen or by a radical selected from the groupconsisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals,and substituted such radicals, such as haloalkyl, alkylene, etc.

Representative of the terminal epoxides which can be used are ethyleneoxide, propylene oxide, 1,2-butylene oxide, 1,2-hexylene oxide, styreneoxide, and epoxides derived from epoxidation of linear olefines, such asfor example octadecene-1,2-epoxide. Examples of useful substitutedepoxides are epichlorohydrin, epibromohydrin, allyl glycidyl ether,butadiene monoxide, vinyl-cyclohexene monoxide, ethyl epoxy oleate,glycidyl acrylate, glycidyl methacrylate, ethyl glycidyl ether, methylglycidyl ether, and epoxides derived from terpenes by epoxidation suchas pinene epoxide. In some instances glycidol is also useful.

Internal epoxides, such as 2,3-butylene epoxide may also be usedalthough they may react at a somewhat slower rate and require longerreaction times.

Useful four-membered cyclic ethers comprise oxetanes and substitutedoxetanes. Especially useful are oxetanes having from 3 to 6 carbon atomsand from zero to 3 halogen atoms selected from the class of chloro andbromo radicals. Examples of useful four-membered cyclic ethers aretrimethylene oxide or oxetane itself, and sub- Stituted oxetanes, suchas Z-methyl oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane,2,4-dimethyl oxetane, 3, 3 bis (chloromethyl) oxetane, and3,3-bis-(brom0- methyl)-oxetane.

The most preferred cyclic ethers for use in the invention are ethyleneoxide and propylene oxide. Both of these are very reactive and arereadily available. Mixtures of cyclic ethers may be employed and arefrequently useful.

Multifunctional epoxides, having more than one epoxy group, may beemployed in admixture with monoethers if partially or completelycross-linked compositions are desired. Diepoxides of 4 to 21 carbonatoms are especially useful in combination With monoepoxides for thispurpose. Representative useful polyepoxides are vinylcyclohexenedioxide, dicyclopentadiene diepoxide, butadiene diepoxide,epoxymethylcyclohexylmethyl(epoxymethylcyclohexylcarboxylate),epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseedoil, glycidyl ethers of glycerol, bisphenol A-diglycidyl ether, butyleneglycol diglycidyl ether, alloocimene dioxide, and similar materials.

The anhydrides which are contemplated for use in the present inventionare cyclic anhydrides, e.g. those having the structural group Bothmonoand polycyclic anhydrides of organic polycarboxylic acids which arecapable of forming a cyclic anhydride can be used in the process, andthey can be aromatic, alicyclic, or aliphatic saturated or partiallysaturated anhydrides. Such anhydrides having from four to fourteencarbon atoms and from zero to six chloro or bromo substituents areespecially useful, e.g. in which R is a hydrocarbon radical having from2 to 12 carbon atoms and from zero to six chloro or bromo substituents.The use of cyclic monoanhydrides is particularly preferred. Especiallythose derived from 1,2-dicarboxylic acids are very suitable. Thoseanhydrides which are presently considered most useful in the process arephthalic anhydride, maleic anhydride, succinic anhydride, and 3, 4,5,6tetrachlorophthalic anhydride. Examples of other cyclic anhydrides whichare useful are 3,4,5, 6-tetrahydrophthalic anhydride, 3,4,5,6tetrabromophthalic anhydride, hexahydrophthalic anhydride,1,4,5,6,7,7-hexachlorobicyclo (2,2,1) 5 heptene 2,3 dicarboxylic acidanhydride, hereinafter called Chlorendic anhydride, itaconic anhydride,glutaric anhydride, diglycollic acid anhydride, and 2,2-diphenyldicarboxylic acid anhydride, hereinafter called diphenic anhydride.

Examples of useful cyclic polyanhydrides are trimellitic anhydride andpyromellitic anhydride.

The halogenated anhydrides are useful for the preparation of polymerswith self-extinguishing properties. It is to be understood that cyclicanhydrides other than those named can be used in the process. Also, asingle anhydride, or mixtures thereof, can be used.

Linear polycarboxylic acid anhydrides, such as polyadipic polyanhydride,polyazelaic polyanhydride, and polyisophthalic polyanhydride andpolyterephthalic anhydride can be employed, but their lower reactivity,higher cost and broadening effect on the polymer molecular weightdistribution makes their use less desirable.

Both monoand polyfunctional aldehydes can be used in the process, andthey can be aliphatic, alicyclic, aromatic or heterocyclic in nature.Both saturated and unsaturated aldehydes are useful. The lower aliphaticaldehydes (which includes formaldehyde) and the phenyl-substituted loweraliphatic aldehydes appear most suitable. Lower alkanals, loweralkenals, lower alkynals, phenyllower alkanals and phenyl-lower alkenaisare subgeneric groups of aldehydes of especial interest in thisinvention. Preferred are those aldehydes having from one to 12 carbonatoms and from 0 to 3 halogen substituents such as chloroor bromoradicals. Aldehydes which are at present considered to be particularlyuseful in the process are'formaldehyde, acetaldehyde, benzaldehyde,trimethylacetaldehyde, terephthaldialdehyde, trichloroacetaldehyde,hereinafter called chloral, and tribromoacetaldehyde, hereinafter calledbromal, as Well as acrolein, crotonaldehyde and cinnamylaldehyde.Examples of other useful aldehydes include propionaldehyde,butyraldehyde, 2-ethyl hexaldehyde, isobutyraldehyde, isodecaldehyde,methacrolein, and tetrahydrofurfuraldehyde.

Monomeric aldehydes are preferred for use as reactants. The aldehydecomponent may be introduced in the form of the cyclic aldehyde polymer,such as trioxane or paraldehyde, but it is not known whether thealdehyde reacts in this polymeric form or whether dissociation to themonomeric aldehyde takes place under the reaction conditions.

Especially preferred for use in the present invention are the loweraliphatic aldehydes having from one to six carbon atoms and from zero to3 halogen atoms. These aldehydes are more reactive than the highermolecular weight aldehydes and combine more readily. Chloral and bromalare particularly useful in the production of polymers with flameretardant properties because of their high halogen content, and theirlow cost.

Since the nomenclature applying to aldehydes and aldehyde polymers isnot universally standardized, it should be noted that We have hereinemployed the nomenclature used in Formaldehyde by J. F. Walker, ReinholdPublishing Co. According to this reference, paraformaldehyde, orparaform, is a mixture of linear polyoxymethylene glycols containing91%99% formaldehyde and generally has the formula HO(CH -O) -H with n inthe range of about 8-l00. Also, in this reference the cyclic trimer offormaldehyde is called trioxane or trioxymethylene while the cyclictrimer of acetaldehyde is paraldehyde.

The use of formaldehyde as a comonomer together with an unsaturatedanhydride, such as maleic anhydride, and

a lower alkylene oxide is particularly advantageous in preparingpolymers with improved color.

If the cyclic ether, the cyclic anhydride and the aldehyde are reactedtogether in the absence of a polymerization starter, aldehydes having atleast one hydrogen atom on the carbon atom next to the aldehyde group,e.g. those aldehydes having the skeletal structural formula where theresidual valenccs may be satisfied by hydrogen or hydrocarbon radicals,should advisably be employed to obtain satisfactory reactivity.

If difunctional aldehydes, such as terephthaldialdehydc, are used ascomonomers, then the resulting polymers are branched, and if asufficient amount of these multifunctional reactants is used, across-linked infusible product results. Similarly, multifunctionalepoxides or dianhydrides may also be used as desired to yield branchedor cross-linked products.

Since the reaction of the cyclic anhydride, the cyclic other and thealdehyde is relatively slow, a polymerization starting material isadvisably included in the anhydride, cyclic ether, and aldehydecomonomer mixture. Compounds capable of starting the polymerization aresubstances which contain one or more groups capable of forming ester,ether, or acetal groups. Suitable polymerization starters which can beused comprise the group consisting of water, ammonia, inorganic acidscapable of effecting the ring opening reaction of cyclic ethers andanhydrides, and organic compounds having at least one radical selectedfrom the group consisting of hydroxyl, carboxyl, and sulfhydrylradicals. Organic compounds having at least one amino radicalsubstituent can also be employed.

Among the inorganic acids those containing hydrogen, and particularlythe monomeric phosphorous-containing acids are preferred. It is to beunderstood, however, that inorganic acids which destructively decomposeorganic compounds, such as nitric acid, are advisably not employed.Suitable inorganic acids are hydrogen fluoride, hydrogen chloride,hydrogen bromide, hydrogen sulfide, hydrogen cyanide, phosphorous acid,phosphoric acid, and boric acid. A phosphorous-containing orboron-containing polymerization starter is particularly useful when thefinal product should have flame-retarding properties.

Organic polymerization starters are compounds containing one or moresubstituents selected from the group consisting of OH, COOH, SH and NH;radicals. Starters having from two to six such radicals are especiallypreferred. Suitable organic polymerization starters comprise alcohols,carboxylic acids, hydroxy-carboxylic acids, phenols, mercaptans,thiocarboxylic acids, amines and amino alcohols. Among the organicpolymerization starters, those having alcoholic hydroxyl groups, such asthe aliphatic alcohols, ether alcohols, and saccharides are preferred.Especially preferred are aliphatic diols and triols, since they resultin compositions with good color and viscosity characteristics.Polymerization starters having amino radicals, such as NH or NH, can beused, but are least preferred since they frequently lead to undesirablecolor formation and also tend to lower the degree of polymerization inthe polyether linkage, e.g. to decrease the length of the polyethersegments.

Mixtures of polymerization starters, in particular aqueous or alcoholicmixtures may be used to advantage. Examples of very useful mixtures arewater-polyol, and water-saccharide mixtures having from one to 80percent by weight of water, and polyol-saccharide mixtures having from 5to 90 percent by weight of polyol.

Particularly useful polymerization starters are those having alcoholichydroxyl groups. One group of very useful alcoholic polymerizationstarters comprises aliphatic alcohols having from one to 18 carbon atomsand from one to eight hydroxyl groups. Particularly desirable are thealiphatic diols having from tWo to 18 carbon atoms,

and the ether glycols of 4 to 15 carbon atoms. Polyols having from threeto six carbon atoms and from three to six hydroxyl groups are alsouseful since theylead to higher-molecular weight, high-functionalityproducts faster. Polymeric alcohols, such as polyvinyl alcohol andpartially hydrolyzed polyvinyl acetate, for example, may also functionas polymerization starters. Polyether alcohols having from one to morethan eight hydroxyl groups and a molecular weight ranging from about onehundred to about 5000 are also useful starters.

Representative alcoholic polymerization starters that can be used aremonoand poly-hydroxy-containing alcohols such as methanol, ethanol,propanol, butanol, pentanol, hexanol, stearyl alcohol, benzyl alcohol,ethylene glycol, propylene glycol, butylene glycol, diethylene glycol,tricthylcne glycol, tetraethyene glycol, dipropylene glycol,tripropylcne glycol, dibutylcne glycol, tributylene glycol,1,12-octadecanediol, glycerol, trimethylol ethane, trimethylol propane,triricinolein (castor oil), pentaerythritol, dipentaerythritol,tripentaerythrirtol, sorbitol, xylitol, mannitol, and inositol.Commercially available mixtures of glycerol, sorbitol and intermediatealcohols are especially useful. Triethanolamine and tripopanolamine arealso of use. Oxyethylene and oxypropylene adducts of glycerol andtrimethylol propane having molecular Weights of about 250 to 3000 andoxyalkylene adducts of sorbitol having molecular weights of up to about2000 have also been found to be useful.

Saccharides comprise another group of useful polymerization starterscontaining alcoholic hydroxyl groups. Saccharides ranging from themonosaccharides, such as xylose and dextrose, through disaccharides,such as sucrose and lactose, to trisaccharides, such as rafiinose and tohigher polysaccharides such as alpha-cyclodextrin, beta-cyclodextrin,and gamma-cyclodextrin may be used. Especially useful are the monoanddi-saccharides having from five to twelve carbon atoms and from four toeight hydroxyl groups. Derivatives such as alpha-methyl glucoside,ethylene glycol diglucoside, and the like may also be employed aspolymerization starters. saccharides other than those named may be used.Polymerization starters of less well -defined composition, such asmolasses, corn syrup, cornstarch, potato starch and various linear andbranched dextrin may be employed. With the more difiicultly solublematerials the more readily soluble portions are generally utilized. Somepolysaccharides may hydrolyze to lower molecular-weight materials underthe acidic conditions of the reaction when water is present.

As mentioned above, water has also been found to be a usefulpolymerization starter and it has been found that the hydrates of polyoland saccharides may also be used as well. Examples of useful hydratesare those of dextrose, lactose, rafiinose, sorbitol and others.

Examples of phenolic hydroxy-containing compounds which may be employedare phenols having from 6 to 15 carbons and from one to three phenolichydroxyl groups, such as phenol, cresol, xylenol, resorcinol, catechol,phloroglucinol and 2,2-bis(4-hydroxyphenyl)-propane.

Organic carboxylic acids and hydroxy-carboxylic acids constitute anothergroup of useful polymerization starters. Carboxylic acids which havebeen used are those having from 2 to 54 carbon atoms and from one tofour carboxylic acid radicals. Very useful starters are saturatedaliphatic acids having from one to 18 carbon atoms, such as for exampleacetic acid, propionic acid, butyric acid, succinic acid, glutaric acid,adipic acid, tricarballylic acid and stearic acid. Unsaturated aliphaticacids having from three to 54 carbon atoms and from one to three doublebonds may also advantageously be employed. Representative of such acidsare acrylic acid, methacrylic acid, oleic acid, aconitic acid, maleicaid, fumaric acid, linoleic acid, linolenic acid, dilinoleic acid andtrilinoleic acid. Aromatic acids, such as benzoic acid, phthalic acid,isophthalic acid, terephthalic acid, pyromellitic acid and trimelliticacid may also be used.

Examples of hydroxy-carboxylic acids which have been employed are thosehaving from 2 to 18 carbons, from one to 5 hydroxyl groups and from oneto three carboxyl groups, such as hydroxyacetic acid, citric acid, malicacid, tartaric acid, 12-hydroxyl stearic acid, ricinoleic acid andgluconic acid. Acidic natural products, such as gum copal, gum dammarand abietic acid may also be used. Other available carboxylic acids andhydroxy-carboxylic acids can be used.

Sulfhydryl-group-containing compounds useful as polymerization starterscomprise aliphatic monoand poly-thiols, especially algyl mercaptanscontaining from one to 12 carbon atoms, the ester derivatives ofaliphatic mercaptoalkyl carboxylic acids, such as alpha-mercaptoaceticacid and beta-mercaptopropionic acid having from 3 to 24 carbon atom andfrom one to siX sulfhydryl groups, and thiophenols. Examples ofsulfhydryl compounds that may be employed include such compounds asmethyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan,monothio-, dithio-, and trithioglycerol, pentaerythritoltetrakis betamercaptopropionate, pentaerythritol-alpha-mercaptoacetate, glyceroltrisbeta mercaptopropionate, glyceroltria-alpha-mercaptoacetate,sorbitol-beta-mercaptopropionate, sorbitol-alpha mercaptoacetate(various esters), and thiophenol and thiocresol. Thiokol-type polymershaving free sulfhydryl groups and molecular weights of generally notmore than 10,000 may be employed.

Examples of amines which can be employed as polymerization starters areprimary and secondary amines having from 1 to 18 carbon atoms and 1 to 5amino or imino groups. Examples are mono and di-methylamine, monoanddi-ethyl amine, butyl amine, morpholine, piperazine, ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene pentamine,laurylamine, stearylamine, ethanolamine, diethanolamine, andisopropanolamine.

The copolymerization between the cyclic anhydride, the cyclic ether, thealdehyde or its cyclic polymer, and desirably a polymerization starter,is effected by bringing the reactants together, in intimate admixture atelevated temperature, and advisably at superatmospheric pressure. Thepolymerization process can be effected batch-wise in a closed vessel,such as an autoclave equipped with agitation, or under continuousreaction conditions in a tubular reactor at elevated temperature. In thepreferred mode of operation all reactants are combined initially beforeheating the reaction mixture. It is to be understood, however, that theentire amount of cyclic ether or all of the anhydride or aldehyde doesnot have to be present at the start of the reaction but that thesereactants may be suitably added in a few sizable portions during thecourse of the polymerization. Such a mode of operation is especiallysuitable if it is desired to incorporate particular monomer residues atspecific locations in the polymer chains. Regardless of the mode ofoperation it is, however, advisable that the total amount of thepolymerization starter is present at the start of the reaction. It isfurther very advisable to conduct the polymerization in a manner suchthat a substantial concentration of the cyclic ether and the aldehyde ispresent intimately admixed with the other reactants during the time inwhich a major proportion of the polymerization takes place. A mode ofoperation in which the aldehyde or the cyclic ether is continuouslyadded in a large number of small increments may be employed, but is notfavored since such a mode of operation does not result in the formationof acetal and ether segments having desirably large degrees ofpolymerization. If polymerization starters are used which undergounwanted side reactions with aldehydes, the polymerization starter mayfirst be reacted with a small fraction of the total amount of the cyclicether and the cyclic anhydride to form a hydroxylor carboxyl-terminatedpolymer and the aldehyde is introduced subsequently along with theremainder of the cyclic ether and anhydride.

Depending on the reactants and temperatures employed, the polymerizationis completed in from a few minutes to a few hours. A temperature ofabout 70 C., and preferably of C. or higher is generally used, althougha temperature above 225 C. is generally not required and leads toadverse results. The most suitable temperatures for the process areabout C. to 220 C. and advisably about to 200 C. However, lower andhigher temperatures can be used as warranted by the reactants used. Ifsaccharidcs are used as polymerization starters, the reaction issuitably conducted within a temperature range of 120 to C. If strongacids, such as phosphorous-containing acids, are used as starters, or ifhalogenated anhydrides, such as chlorendic anhydride or dichloromaleicanhydride, are employed the temperature necessary to achieve reaction isconsiderably lowered. For example, polymers from chlorendic anhydride, apolyol, formaldehyde and an epoxide are formed at a satisfactory rate at80 C.

Although some water can form in the process because of the startinmaterial used, it is not essential to remove the water during theprocess for the polymerization to proceed. Since it is not essential toremove small molecules such as water or alcohol to have the reactionproceed to completion, the process can be run in a completely closedsystem thus avoiding any losses of volatile reaction components.Superatmospheric pressure, such as autogeneous pressure, is used for thepolymerization although even higher pressures are very suitable inproducing these ternary coploymers. The pressure used has to be at leastequal to or higher than the vapor pressure of the reaction mixture atthe reaction temperature. A minimum pressure of 1.5 atmospheres isadvisably used, and in most cases where lower epoxides are used,reaction pressures will vary from at least about 50 pounds per squareinch to about 300 pounds per square inch.

The process of this invention does not require the use of a catalyst.However, strong acids (i.e., those which ionize at least as much asbromoacetic acid) have been found to act as catalysts, and if strongacids or anhydrides derived from strong acids are used as reactants theprocess becomes autocatalytic. Phosphoric acid, phosphorous acid,dichloromaleic anhydride, tetrachlorophthalic anhydride and chlorendicanhydride are some that can be used as catalysts. A substantial increasein therate of reaction is also observed if impure chloral contaminatedwith small amounts of trichloroacetic acid is used as a reactant. Sinceno catalytic residues remain in the final polymer, there is no need forpurification. Furthermore, additional post-treatment steps needed inother processes to remove catalyst residues are not required in thisinvention.

In preparing these random copolymers the mol ratio of cyclic ether tocyclic anhydride may be varied from about 1:1 to generally not more thanabout 10:1, and more commonly not more than 6:1. The lower mol ratiostend to give predominantly carboxylic acid end groups, and the highervalues hydroxyl end groups. The nature of the end groups is determinedby the relative concentration of cyclic ether and anhydride in theterminal stages of the reaction. If cyclic ether predominates, hydroxylend groups will result. If the anhydride con- I centration is stillsubstantial, then carboxylic acid end groups will be formed. The amountof aldehyde employed will constitute at least one percent, and usuallyat least five percent and more frequently at least ten percent to notmore than 99 percent and usually not more than 95 and more commonly notmore than 90 percent by weight of the total reactant mixture.

The composition of a binary polyether-polyester copolymer is dependenton the ratio of cyclic ether to anhydride in the reaction mixture andthe average length of the polyether segments is a direct function ofthis ratio.

When an aldehyde is used as a comonomer together with cyclic ethers andanhydrides the average degree of polymeriaztion of the polyetherlinkages is necessarily decreased because of the interspersing of acetallinkages among the ether links. The shortening of these polyetherstructures is directly dependent on the relative amount of aldehydeincorporated. However, it seems that the relative amounts of anhydrideand epoxide incorporated into the polymer are actually relativelyindepedent of the relative amount of aldehyde present in the reactionmixture, but are only dependent on the ratio of epoxide to anhydrideemployed.

Suitable amounts of polymerization starter employed in the process willrange from about 0.1 percent to more than percent by weight of the totalreactant mixture. In general, larger amounts of higher-molecular-weightstarting materials are used than those of lower molecular weight. Whencompounds of low molecular weight, such as water, or hydrogen sulfide,are used, the amount of starter will generally not exceed 10 percent byweight of the total reactant mixture. In some instances involvingstarters of high equivalent weight, or polymers of low equivalentweight, the proportion of starter may exceed 50 percent by weight of thetotal reactant mixture. For example, if a low-moleculer-weight polymeris formed by reacting an epoxide, an aldehyde, and an anhydride usingstearyl alcohol as the starter, about 50 percent of the total polymerweight could be derived from the starter residue. The importantconsideration in determining the amount of starter to be used inpreparing thermoplastic random ternary copolymers is the ratio of thepolymer equivalent weight desired to the starter equivalent weight. Theequivalent weight of the starter is computed by dividing the startermolecular weight by the number of functional groups capable of startingthe polymerization reaction. The equivalent weight of the polymer iscomputed by dividing the polymer molecular weight by the number ofpolymer chain-end groups. Thus the ratio of the weight of starter usedto the total weight of the polymer formed is the same as the ratio ofstarter equivalent weight to the polymer equivalent weight.

The resulting random ternary copolymers may vary from viscous liquidsand glassy or crystalline thermoplastic solids to cross-linked infusibleresilient or non-resilient solids. The physical form of these ternarycopolymers can be varied within wide limits by appropriate choice of thereactants allowing extensive control over regularity, bulkiness,polarity, stiffness and branching. The use of aldehydes as comonomersallows an additional degree of freedom in tailoring the properties, suchas rigidity or flexibility, of the polymer chains. If an unsubstitutedlowmolecular-weight aldehyde or epoxide, such as formaldeahyde orethylene oxide, is used as a reactant the resulting linear, unhinderedacetal or ether segments impart more flexibility to the polymer chain.It the aldehyde or epoxide monomer has bulky substituents, however, theresulting polymer chains will be stiffened by the presence of thependant bulky groups. Likewise, the use of saturated aliphaticanhydrides, such as succinic anhydride, results in flexible polymerchains and the use of anhydrides with ring structures, such as phthalicanhydride, results in considerable stiffening of the polymer chains.Thus the rigidity and flexibility of the polymer chains can be easilycontrolled by selection of the monomers.

The process of this invention permits the use of monomers of lowerinitial cost than previous processes. The use of large amounts ofaldehydes in the preparation of these ternary copolymers appearsparticularly attractive. Specifically, formaldehyde and acetaldehyde aresubstantially less expensive than the other cyclic comonomers, and thusa polymer containing a large proportion of acetal linkages can be veryadvantageous from an economic point of view. In addition,trichloroacetaldehyde is a considerably less expensive source ofchlorine than are the chlorinated acid anhydrides. Thus, the use ofthese inexpensive aldehyde monomers in combination with epoxides andcyclic anhydrides, plus the simplicity, ease and speed in operation ofthe process results in considerable savings in the cost of the finalpolymer.

The total molecular weight of the random ternary copolymers may varyover a wide range and will depend on the quantities and nature of thereactants employed. There appears to be no upper limit on the molecularweights which can be achieved and molecular weights as high or as low asdesired may be obtained. Thermoplastic com positions of interest willgenerally have molecular weights varying from about 500 to not more thanabout 50,000, and frequently to less than 30,000. The equivalent weightof poly-functional compositions will be determined by the nature of thepolymerization starter and the molecular weight.

Because of the nature of the addition polymerization reaction by whichthey are prepared, the novel thermoplastic copolymer compositions whichare prepared only from difunctionally reactive cyclic ethers,anhydrides, and aldchydes, in the absence or presence of apolymerization starter according to this invention are furthercharacterized by having a relatively narrow molecular weightdistribution, that is, the difierences in molecular weight betweenindividual polymer molecules are relatively small, with the ratio ofweight-average to number-average molecular weights being less than 1.5.Under theoretical conditions, ring-opening polymerizations generallylead to polymers with molecular-weight distributions of a type referredto as Poisson-type which are much narrower than the distributions of thegeometric type characteristic of polymers produced by polycondensationprocesses. Such thermoplastic compositions also exhibit desirably lowviscosities.

The molecular Weights of partially and completely crosslinkedcompositions will be higher and will increase with the degree of crosslinking. The ratio of weight-average to number-average molecular weightwill also increase with cross linking.

According to a further aspect of the invention, there are provided novelternary copolymers having ester, ether and acetal groups but with theacetal groups present in the form of regular blocks, rather thandistributed randomly, and with the acetal blocks bounded by or separatedfrom each other by blocks composed of random polyester-ether copolymer.The production of such block terpolymers incorporating preformedpolyacetal blocks is based on the discovery that polyacetals havingactivehydrogen-containing substitutents and of the formula G- CH-O Gwhere R" has the previously assigned meaning, m is an integer varyingfrom 5 to 500 and G is a radical of the group consisting of OH, COOH,NH, NH and SH radicals, can act as polymerization starters for theaddition copolymerization of epoxides and anhydrides and thereby becomeincorporated as polyacetal blocks into the polymer chains.

In this specific embodiment of the present invention these polymers areproduced by reacting together (1) a cyclic ether selected from the groupconsisting of epoxides and oxetanes (2) an anhydride selected from thegroup consisting of linear and cyclic anhydrides of organicpolycarboxylic acids and (3) a linear polyacetal terminated withactive-hydrogen containing end groups. Especially preferredpolymerization starters are the polyacetals having terminal hydroxylgroups. In addition to the polyacetal, other active hydrogen-containingpolymerization starters previously described herein may be employed inadmixture. The mode of operation, temperature, pressure and nature ofthe cyclic ether and cyclic anhydride are essentially the same as in theprocess described herein using monomeric aldehydes. Cyclic anhydridesand cyclic others as named herein previously can be used in this 13embodiment. Linear anhydrides previously listed may also be employed.

Examples of some of the polyacetals that can be used arepolyoxymethylene, polyacetaldehyde, polychloral, and polybromal.Suitable polyacetals will have molecuar weights of at east 200, andusually at least 400 and preferably at least 1000. The polyacetals areprepared by methods known to the art. Particularly preferred for use inthe present invention are hydroxyl-terminated polyoxymethylenes having avery low methoxyl content and having molecular weights ranging fromabout 1000 to about 10,000 and higher. Suitable high-molecular weightpolyoxymethylenes may be prepared by methods known to the art, such asthe polymerization of pure formaldehyde, free of water and methanol, ininert solvents in the presence of amine catalysts, or the polymerizationof trioxane with Lewis acid catalysts. A preferred inexpensive source ofsuitable polyoxymethylenes is provided by commercially availablemethanol-free paraformaldehyde, which is prepared from formaldehyde madeby the oxidation of hydrocarbons rather than the oxidation of methanol,and which has 3 formaldehyde content of at least about 90, andpreferably, about 95 percent by weight, with the remainder consisting ofwater. The molecular weight of such commercially available methanol-freeparaform may be increased by heating, preferably below the meltingpoint, either concurrent with, or followed by the application of avacuum, to remove water. The progress of this increase in molecularweight is conveniently followed by noting the accompanying increase inmelting point. References describing the increase in molecular weight byheating include Brown and Hrubesky, Ind. Eng. Chem., 19, 217 (1927),Auerbach and Barschall Studien uber Formaldehyde-Die Festen Polymerendes Formaldehyds pp. 7-9, Berlin, Julius Springer (1907) and Walker, I.Am. Chem. Soc. 55, 2823-4 (1933).

These hydroxyl-terminated polyoXymethylenes prepared by the dehydrationof methanol-free paraformaldehyde, and having molecular weights in therange of 2000- 10,000, and even higher, are particularly cheap anddesirable raw materials for the preparation of the block terpolymers ofthe present invention. In preparing these block terpolymers, the molratio of cyclic ether to anhydride generally employed will vary fromabout 2:1 to about 6:1, and the polyacetal starter will constitute fromabout to 98 percent by weight of the total reaction mixture, andfrequently from about 20 to 90 percent by weight.

If only difunctionally reactive cyclic monoethers and cyclicmonoanhydrides are employed, one polyacetal block will becomeincorporated into each polymer chain. The polyacetal withactive-hydrogen end groups serves as a linear, high-molecular-weightnucleus to which is attached chains of polyester-ether by reacting withthe cyclic anhydride and the cyclic ether. The final product has a blockpolymer structure, with a, block of polyacetal separating blocks ofpolyester-ether. The polymer chains of the resulting thermoplastic blockpolymer can be represented by the schematic sequence E-A-B-A-E, whereinE are active-hydrogen-containing end groups selected from the groupconsisting of hydroxyl and carboxyl radicals. A represents a randompolyester-ether copolymer block composed of one or more recurring unitsof the structural formula and B is a polyacetal block of the structuralformula RI! (J1HO)m wherein R, R", and n have the previously assignedmeaning, R is a hydrocarbon radical having from 2 to 12 carbon atoms andfrom zero to six halogen substituents of the group consisting of chloroand bromo radicals and is identical with the radical connecting twocarboxylic acid carbonyl functions in a dicarboxylic acid and m' is apositive whole number ranging from about 5 to generally not more than500, and frequently to not more than 100.

Preferred compositions are those in which R is 1,2- ethylene or1,2-propylene and R is selected from 1,2- ethylene, 1,2-ethenylene(CH=CH), 1,2-phenylene, 3,4,5,6-tetrachloro-1,2-phenylene,3,4,5,6-tetrabromo-1,2- phenylene, 3,4,5,6-tetrahydro-1,2-phenylene andhexachlorobicycloheptenylene.

Desirable compositions will generally contain from at least about 2percent and usually not less than five percent by weight of A blocks upto not more than about 95 percent by weight and frequently not more thanpercent of A blocks. The weight fraction of B blocks will vary fromabout 5 percent, and usually from about '10 percent by weight, to notmore than 98 percent and generally not more than percent by weight. Ofthe weight fraction of the polymer which is the polyester-ethercopolymer, the residues of cyclic ether and anhydride are present insuch a proportion that the molar ratio of R to R will range from about1.25, and usually from 1.5, and preferably from about 2 up to not morethan ten and preferably to not more than six.

For example if the original polyacetal and the final copolymer havehydroXyl endgroups, then the final polymer molecules based upon thepolyacetal chains can be represented essentially as follows:

HO OH q RI! wherein R, R' and R" have the previously assigned meanings,and n is an integer varying from one to about five, and having anaverage value ranging from 1.01 to ten and generally from 1.25 to 6, nis an integer varying from zero to about five, m is an integer varyingfrom about five to five hundred, and usually is less than one hundred,and q is a number having an average value varying from about one togenerally not more than fifty.

Several simplifications have been made in the above representation.Since the polyacetal containing hydroxyl end-groups is somewhat unstableat the reaction temperature, an amount of free aldehyde may be lost fromthe polyacetal by thermal depolymerization and become incorporated intothe polyester-ether portion of the molecule. Consequently the polyacetalportion of the molecule will probably contain less aldehyde units thandid the original polyacetal structure, and the polyester-ether seg mentsmay contain a few acetal members, and it is to be understood that suchminor structural deviations are included within the scope of the generaldescription hereinabove and in the claims.

Block terpolymer compositions having molecular weights as high asdesired can be prepared, however, the thermoplastic products of interestwill generally have a molecular weight of at least 500 and frequentlynot more than 50,000, and preferably not more than 30,000. The averagedegree of polymerization in the ether segments will be at least 1.01 andmay be as high as ten, and will generally vary from about 1.25 to aboutsix.

The above representations are of the polymer based on a nucleus composedof a polyacetal only. Additional active-hydrogen functional compoundsmay be included as nucleus-forming agents.

A relatively high proportion of polyacetal structures may readily beincorporated into polymers prepared by this method. By choosing theproper reactants it is possible in this manner to prepare a polymerwhich is primarily polyacetal in structure and has only relatively smallblocks of polyester-ether end structures. Depending on the originalmolecular weight of the polyacetal chains it is possi- 1 5 ble toprepare block polymers containing more than 90% by weight in the centralpolyacetal block. For example, if the original polyacetal used asstarter has a molecular weight of 10,000, and short polyester-etherchains having molecular weights of 500 are attached to the ends, thenthe polyacetal content of the final polymer is 90.9%.

Polyester-ether-acctals containing a relatively large content ofpolyacetal structure have properties largely dictated by the centralpolyacetal block. Thus such polymers based on polyoxy-methylenes arecharacteristically crystalline, hard and dense, and have the appearanceand feel associated with other known modifications of polyoxymethylene.

The polyester-ether-acetals are chemically and thermally stable. Theyare less sensitive to attack by chemical reagents than are theunmodified polyacetals. The process of reacting a polyacetal with acyclic anhydride and an alkylene oxide is thus a desirable method ofobtaining thermally stable polymers from polyacetals.

The method of preparation of these block copolymers is unique in that itallows coupling together of blocks of polyacetal structure by the use ofa dianhydride or bisepoxide in the polymerization. If only a relativelysmall proportion of such a multifunctional reactant is employed, thenthe resulting polymer is a longer, straight-chain, or slightly branchedstructure incorporating a multiplicity of polyacetal blocks. Such apolymer is tougher, and has a higher melt viscosity than thecorresponding polymer containing only one polyacetal block. If arelatively large proportion of such multifunctional reactants areemployed, then the resulting polymer is highly branched or evencross-linked. Such cross linked structures are infusi- =ble and quitethermally and chemically resistant. These cross-linked structures wouldappear to be the only known representatives of the class ofthermosetting polymers containing large blocks of polyacetal structures.They thus provide a one-step method of making molded articles andshapes. The useful cross-linked compositions will generally have thesame content of polyacetal, cyclic ether, and cyclic anhydride residuesas those of the thermoplastic compositions, except that a portion ofcyclic ether or cyclic anhydride residues consist of residues ofpolyfunctional i.e., functionality of greater than 2, reactants.

The thermoplastic random ternary copolymers described herein possessutility as surface-active agents and as polymeric plasticizers, and theyare particularly useful as resin intermediates. Especially useful inthis regard are the terpolymers containing bromal and chloral residuessince they lead to flame-retardant compositions.

The ternary block copolymers, and the chain-coupled ternary blockcopolymers having a high proportion of internal polyoxymethylenelinkages are useful as highmelting, rigid thermoplastics, especially asmolding and extrusion resins, and as textile fibers.

Both the random and the block ternary copolymers which possess amultiplicity of reactive olefinic double bonds, such as residues ofmaleic or itaconic anhydride may be reacted with unsaturated vinylmonomers, such as styrene, alpha-methyl styrene, vinyl toluene, methylmethacrylate, divinyl benzene and chlorostyrene in the presence of afree-radical initiator or its equivalent to form flexible-to-semi-rigidcasting, laminates and potting compositions. In preparing suchcompositions techniques known to the art are employed.

Another excellent application of the thermoplastic random or blockterpolymers of the present invention is in combination with organicpolyisocyanates as components in polyurethane formulations, such ascoatings, foams, castings, and elastomers. Depending on the terpolymerselected, polyurethanes varying from rubbery, flexible products to hard,cross-linked compositions may be prepared. The hydroxyl-terminatedpolyoxymethylene block terpolymers having easily crystallizablepolyesterether blocks, such as for example polyoxyethylene succinate,may be reacted with organic diisocyanates to form elastomeric fibers. Inthe preparation of polyurethane compositions from the copolymersdescribed herein techniques generally employed in the art are used.

The insoluble, cross-linked terpolymers of the present invention areuseful as casting, laminating and potting resins.

The following examples are presented to illustrate the invention.

Example 1 This example illustrates the preparation of a ternarypolyester-ether-acetal copolymer containing acetal linkages derived fromformaldehyde.

Phthalic anhydride (41.2 grams), glycerol (5.6 grams) and propyleneoxide (44.4 grams) are placed into a stainless steel bomb. Then gaseousformaldehyde (9.0 grams), prepared by pyrolysis of paraformaldehyde, isweighed in, and the bomb is sealed. The bomb is then heated at 132 C.for one hour, 151 C. for another hour and 176- C. for three hours. Theproduct is very viscous, and has an acid number of 3. There is only asmall amount of volatiles present.

Example 2 This example illustrates the preparation of a ternarypolyester-ether-acet-al copolymer containing acetal linkages derivedfrom acetaldehyde.

Phthalic anhydride (44.6 grams), glycerol (5.0 grams), propylene oxide(46.0 grams) and acetaldehyde (7.5 grams) are sealed together in athick-walled glass tube. The tube is heated at C. for one hour andtwenty minutes, at 158 C. for 30 minutes, at 178 C. for 45 minutes andat 189 C. for 40 minutes. The product is viscous, yellow-orange incolor, and has an acid number of 13.

Example 3 This example illustrates the preparation of a ternarypolyester-ether-acetal copolymer in which the acetal linkages arederived from chloral.

Phthalic anhydride (10.1 grams), glycerol (3.1 grams), propylene oxide(10.3 grams) and freshly distilled chloral (25.1 grams) are sealedtogether in a heavy-walled glass tube. The mixture warms slowly becauseof an exothermic reaction. The tube is then heated consecutively at 149C. for three and a half hours and at 159 C. for three hours. The productis an extremely viscous, light-orange product with an acid number of 20.The product is of particular interest because of its high chlorinecontent of 37%.

Example 4 This example illustrates the preparation of apolyesterether-acetal ternary copolymer containing acetal linkagesderived from benzaldehyde.

Phthalic anhydride (13.5 grams), trimethylolpropane (1.5 grams),propylene oxide (15.1 grams), and benzaldehyde (8.8 grams), are sealedtogether in a heavy-walled glass tube. The tube is heated at 143 C. fortwelve hours. The resulting product is a viscous polymer.

Example 5 This example illustrates the preparation of a crosslinked,infusible polymer containing acetal linkages derived fromterephthalaldehyde.

Phthalic anhydride (17.9), tetrachlorophthalic anhydride (1.7 grams),glycerol (2.4 grams), propylene oxide (20.0 grams), andterephthalaldehyde (8.1 grams) are sealed together in a strongheavy-walled glass tube. The mixture is heated at 154 C. for 22 hours.The product is a clear gel at oven temperature, and becomes rigid oncooling. The polymer chains have been cross-linked through theterephthalaldehyde acetal linkages.

Example 6 This example illustrates the preparation of a copolymercontaining acetal linkages derived from acetaldehyde.

preparation Example 7 This example illustrates the use of formaldehydein the preparation of unsaturated polymers with improved color.

Phthalic anhydride (15.1 grams), maleic anhydride (11.8 grams), glycerol(2.5 grams) and propylene oxide (30.6 grams) are placed in a stainlesssteel bomb tube. Then gaseous formaldehyde (5.8 grams) is weighed in andthe bomb is sealed. The bomb is heated at 157 C. for one hour and 20minutes. The product is a viscous fluid with a pale, pinkish-yellowcolor. The color is considerably lighter than that of a polymer preparedwithout formaldehyde.

Example 8 This example illustrates the preparation of a polyurethanefoam from the ternary copolymer prepared in Example 1.

The polymer (19.8 grams) is mixed together with 0.5 grams offluorotrichloromethane, five drops of siliconeglycol copolymer, threedrops of tetramethyl-1,3-butanedia-mine, four drops of stannous octoate,and 0.4 gram of water. Then 2,4-tolylene diisocyanate (8.2 grams) isadded and rapidly stirred in. The resulting foam is cured at 85 C. fortwo hours. The product is a stifl, tough foam which shows no appreciableshrinkage on cooling.

Example 9 This example illustrates the preparation of apolyesterether-acetal based on commercial paraform.

Flake paraform (2.55 grams), phthalic anhydride (0.3 gram), andpropylene oxide (0.4 gram) are sealed together in a glass tube andheated at 190 C. for three hours. The mixture is a colorless,glass-clear fluid melt. On cooling, the mixture solidifies to acolorless, soft wax having an ivory-like luster.

Example 10 This example illustrates the preparation of apolyesterether-acetal based on a polyoxymethylene having a highmolecular weight.

Pure, dry formaldehyde gas is prepared by pyrolyzing paraformaldehyde,and passing the gaseous products through a silica gel column maintainedat C. The gas is then introduced into a solution of 0.2% dimethyloctadecyl amine in cyclohexane. The polymer which precipitates is washedwith ether and dried under vacuum. The resulting polymer has hydroxylend groups and a molecular weight in excess of 10,000.

The above polymer (3.6 grams), phthalic anhydride (0.2 gram), andpropylene oxide (0.3 gram) are sealed in a heavy-walled glass tube andheated at 197 C. for three hours. The product is a clear viscous melt atoven temperature and is a colorless, hard, tough solid at roomtemperature.

Example 11 This example illustrates the preparation of a crosslinkedpolyester-ether-acetal from commercial paraform.

Phthalic anhydride (0.35 gram), flake paraform (2.35 grams) andepoxycyclohexylmethyl-epoxycyclohexyl carboxylate (0.7 gram) are sealedtogether in a heavy-Walled glass tube. The tube is heated to 375 F. forfour hours. The product is a clear gel at oven temperature andcrystallizes to a hard, moderately tough resin at room temperature.

1 8 Example 12 This example illustrates the preparation of apolyesterether-acetal based on polychloral.

Chloral was distilled from powdered calcium oxide. The clear, colorlessdistillate was allowed to stand for several months. During this time asmall amount of white polymer formed on the walls of the vessel. Thisadventitious polymer was filtered and allowed to dry.

The dried polymer (1.5 grams), phthalic anhydride (0.2 gram), andpropylene oxide (0.35 gram) were sealed in a glass tube and heated at160 C. for 55 minutes.

The product was a clear, nearly colorless liquid which is quite viscousat room temperature.

Example 13 Flake paraformaldehyde, having a formaldehyde content of91-92% and a very low content of methanol is dried overnight at roomtemperature under a vacuum of about 0.1 mm. pressure of mercury.

2.73 grams of the vacuum-dried material, 2.30 grams of maleic anhydride,and 3.44 grams of propylene oxide are sealed together in a heavy-walledglass tube, and heated at 165 C. for 4 hr. and 37 min. The resultingpolymeric product is of moderate viscosity and has a very pale yellowcolor. It partially crystallizes on standing at room temperature. Theinfrared spectrum exhibits a strong ester carbonyl absorption 'band.

3.90 grams of this polymer is heated with 0.69 grams of tolylenediisocyanate at 70 C. for 1 /2 hr. The product is a clear, gummy rubber.

Example 14 The vacuum-dried paraformaldehyde of Example 13 is heatedovernight in a sealed tube at 140 C., to increase its molecular weight.Then it is heated at 154 C. for 5 hours in a sealed tube until it justbegins to sinter. This material is then again vacuum dried overnight.

1.27 g. of this treated material, 1.29 g. of maleic anhydn'de, and 1.56g. of propylene oxide are heated at 166 C. for 2 hr. and 33 minutes. Thecolor is pale yellow, and the product crystallizes rather quickly oncooling.

In a second experiment, 1.26 g. of the treated material, 0.32 g. ofmaleic anhydride, and 0.52 g. of butylene oxide are heated at 185 C. for1 hr. and 40 min. There is some condensate of unreacted epoxide as thetube is cooled, and there is also some condensate of unreactedparaformaldehyde in the top of the tube. The cold product is amedium-soft, slightly tacky wax.

Example 15 Powered paraformaldehyde of formaldehyde content, and of verylow methanol content is heated for 18 /2 hr. at C. The product ispartially sintered.

1.40 grams of this material, 1.20 grams of maleic anhydride, and 1.44grams of propylene oxide are heated in a heavy-walled, sealed glass tubeat C. for about 1 hour before the contents fully melt. After 5% hr., theproduct is cooled. The product is pale yellow and extremely viscous. Itbecomes cloudy and partially crystallizes on standing at roomtemperature.

2.47 grams of this terpolymer, 1.09 grams of styrene, and 0.02 gram ofaZ0bis(isobutyr0uitrile) are heated at 70 C. for 2 hr. The cured productis opalescent, and has a Shore A hardness of 85. It is flexible and notbrittle.

Example 16 This example illustrates the use of an aldehyde comonomer tosubstantially reduce the viscosity of a highfunctionality polyol. Theexample, part B, is nearly identical wtih part A except thatprionaldehyde is added to the rectant mixture, and the amount of theother reactants is decreased by 10% (A) In a 1-liter, stirred 316stainless steel pressure vessel was placed 135.7 grams of anhydrousdextrose, 39.8 grams of 99.5% glycerol, 240.4 grams of phthalic 19anhydride, and 494.0 grams of propylene oxide. The vessel was closed,and then heated at 295-340" F. for 3 hr. The exceses propyline oxide wasthen vented. The recovered product weighed 758 grams, and had aviscosity of 408,000 centipoises at 25 /2 C.

(B) In a 1-liter, stirred 316 stainless steel pressure vessel was placed121.4 grams of anhydrous dextrose, 36.7 grams of 99.5% glycerol, 212.5grams of phthalic anhydride, 447.1 grams of propylene oxide, and 71.6grams of propionaldehyde.

The vessel was closed and heated at about 290-330 F. for 4 hr. 40 min.Then the excess epoxide and aldehyde were vented, and the productrecovered. The product was an olive color and weighed 724 grams, about42 grams of which consisted of chemically combined propionaldehyderesidues. The polymer had a viscosity of 80,000 centipoises at 25 /2 C.

Example 17 In a heavy-walled glass tube are combined 0.15 gram oftrimethylolpropane, 1.2 grams of maleic anhydride, 1.4 grams of1,2-butylene oxide and 1.2 grams of 2-ethyl hexaldehyde. The tube issealed, and then heated at 150 C., with intermittent shaking, for 5 hr.23 minutes. The product is a pale yellow homogeneous fluid which has aviscosity of about 100 centipoises at room temperature. The tube is thenopened and heated for about 7 hours at 160 C. to drive off theuncombined reactants. The weight loss is 0.51 gram.

Example 18 The same technique is used in Example 17. The raw materialsare 0.15 gram of trimethylolpropane, 1.15 grams of maleic anhydride,1.65 grams of 1,2-butylene oxide, and 0.95 gram of crotonaldehyde. Thetube is heated for 4 hr. 7 min. at 150 C. The appearance of the productis similar to that of Example 17, but the polymer viscosity is about1000 centipoises at room temperature. The seal is then broken and thereaction mixture heated at 160 C. for about 7 hours until a constantweight is obtained. The weight loss is 0.60 gram.

Example 19 The same technique is used as in Example 17. The rawmaterials are 0.2 gram of trimethylolpropane, 1.25 grams of maleicanhydride, 0.8 gram of propylene oxide, 0.05 grams of triethyl amine and1.65 grams of 2-ethyl hexaldehyde. The tube is heated at 150 C. for 4hr. 9 min. The product has a red-brown color, and on cooling separatesinto two phases. The upper phase, which consists largely of unreacted2-ethyl hexaldehyde, is very fluid and is about 1 ml. in volume. Thus,about /2 of the aydehyde has become chemically combined. The lowerlayer, which is the polymeric product, has a viscosity of severalhundred centipoises.

Example 20 The same technique is used as in Example 17. The rawmaterials are 0.40 gram of polyethylene glycol of 200 mol. wt., 1.25grams of maleic anhydride, 0.75 gram of propylene oxide, 0.05 gram ofN-methylmorpholine and 1.30 grams of 2-ethyl hexaldehyde. The tube isheated for 32 minutes at 150 C. The product is black, and on coolingseparates into two phases, the upper one of about 1 ml. volume. Theviscosity of the lower layer is about 1000 centipoises.

Example 21 The same technique is used as in Example 17. The rawmaterials are 0.2 gram of citric acid monohydrate, 0.95 gram of maleicanhydride, 1.15 grams of propylene oxide, and 1.1 grams of 2-ethylhexaldehyde. The tube is heated at 150 C. for 4 hr. 50 min. The productis a pale orange homogeneous fluid with a viscosity of several hundredcentipoises at room temperature. The weight loss determined as inExample 17 is 045 gram after 7 hours at 160 C.

20 Example 22 The same technique is used as in Example 17. The rawmaterials are 0.45 gram of polyoxyethylene glycol of mol. Wt. 200, 1.05grams of succinic anhydride, 1.0 gram of propylene oxide, and 1.7 gramsof 2-ethyl hexaldehyde. The tube is heated at 150 C. for 4 hr. 2 min.The product is nearly colorless, and at room temperature separates intotwo very fluid phases, the upper phase amounting to about 0.75 ml., andconsisting largely of unreacted aldehyde. The lower phase is very fluidand consists of the polymeric product.

Example 23 The same technique is used as in Example 17. The rawmaterials are 0.45 gram of linseed oil fatty acid, 1.25 grams oftetrahydrophthalic anhydride, 1.4 grams of propylene oxide, and 0.9 gramof 2-ethyl hexaldehyde. The tube is heated at 150 C. for 3 hr. 38 min.The product is a colorless, fluid polymer of low viscosity.

Example 24 The same technique was used as in Example 17. The rawmaterials are 0.35 gram of phosphoric acid, 1.7 grams oftetrachlorophthalic anhydride, 2.4 grams of epichlorohydrin, and 0.9gram of 2-ethyl hexaldehyde. The tube is heated at C. for 3 hr. 13 min.The product is a homogeneous, pale pink fluid with a viscosity ofseveral thousand centipoises.

Example 25 The same technique was used as in Example 17. The rawmaterials are 0.45 gram of trimethylolethane tris (thioglycolate), 1.4grams of phthalic anhydride, 0.9 gram of propylene oxide, and 1.2 gramsof 2-ethyl hexaldehyde. The tube is heated at 150 C. for 3 hr. 54 min.The product is pale yellow, and has a viscosity of about 500centipoises.

Example 26 The same technique is used as in Example 17. The rawmaterials are 0.25 gram of trimethylolpropane, 1.3 grams of phthalicanhydride, 2.9 grams of vinyl cyclohexene monoxide, and 0.8 gram of2-ethyl hexaldehyde. The tube is heated at 150 C. for 3 hr. 36 min. Theproduct is very pale yellow, and has a viscosity of greater than 10,000

centipoises at room temperature.

Example 28 The same technique is used as in Example 17. The rawmaterials are 0.2 gram of anhydrous sorbitol, 1.45 grams of phthalicanhydride, 1.35 grams of propylene oxide, and 1.95 grams of 2-ethylhexaldehyde. The tube is heated at 150 C. for 4 hr. 27 min. The cooledproduct is colorless and has a viscosity of about 100 centipoises atroom temperature. On heating the opened tube at C. for 7 hours, theweight loss is 1.6 grams, indicating that about 0.4 ram of aldehyde hasbecome combined.

Example 29 The same technique is used as in Example 17. The rawmaterials used were 0.35 gram of trimethylolpropane, 1.45 grams ofphthalic anhydride, 2.05 grams of propylene oxide, and 1.15 grams ofmethacrolein. The tube was heated at 127 C. for 3 hr. 54 min. Theproduct was very pale yellow and had a viscosity of about 100centipoises. The tube was then opened and heated at an elevatedtemperature until a constant weight had been obtained. The weight lossdue to evaporation of volatile components was 1.195 grams An infra-redspectrum of this devolatilized polymer showed significant absorptionbands at 5.45, 5.68, 10.35, 11.1, and 12.7 microns which were notpresent in the spectrum of the polymers of Examples 16A and 16B.

Example 30 The same technique is used as in Example 17. The rawmaterials used were 1.6 grams of phthalic anhydride, 1.75 grams ofpropylene oxide, and 1.15 grams of propionaldehyde. The tube was heatedat 127 C. for hr. 27 min. The product was a clear, colorless, somewhatviscous fluid. On opening the tube, the contents partially crystallized.The opened tube was then heated at an elevated temperature until aconstant weight was obtained. The weight loss, presumably'due toevaporation of unreacted aldehyde and epoxide, was 2.00 grams, thusindicating that at least about 0.9 gram of aldehyde and epoxide becamechemically combined.

Example 31 Example 11 is repeated using an equal amount of polyadipicpolyanhydride in place of the phthalic anhydride. The reaction issomewhat slower, and the product is somewhat more colored, but theresults are otherwise similar to those of Example 11.

Example 32 The polyester-ether-acetal preparation of Example 13 isrepeated using polyazelaic polyanhydride in place of the maleicanhydride. The materials used are 2.82 grams of the vacuum-driedmaterial, 3.50 grams of propylene oxide, and 3.99 grams of polyazelaicpolyanhydride. The reaction proceeds similarly to that of Example 13 andthe product is also similar.

We claim:

1. The process of producing ternary copolymeric compositions containinga multiplicity of ester, ether and acetal units in substantially randomdistribution in the polymer chains, which consists essentially ofreacting together in a closed system at a temperature of about 70 C. to225 C. (l) a cyclic ether selected from the group consisting of epoxidesand oxetanes, (2) a cyclic anhydride of an organic polycarboxylic acidhaving from four to fourteen carbon atoms and from zero to six halogensubstituents selected from the group consisting of chloro and bromoradicals, (3) an aldehyde, and (4) from 0 to 50 percent by weight of thetotal reactant mixture of a polymerization starter selected from thegroup consisting of water, ammonia, hydrogen-containing inorganic acidscapable of effecting the ring-opening reaction of (1) and (2), andorganic compounds having at least one radical selected from the groupconsisting of hydroxyl, carboxyl, sulfhydryl, and amino radicals, andmixtures thereof, the ratio of mols of reactive cyclic ether groups insaid cyclic ether to mols of anhydride groups in said polycarboxylicacid anhydride ranging from one-to-one to about ten-to-one, and theamount of aldehyde varying from about one percent to about 99 percent byweight of the total reactant mixture.

2. The process of claim 1 in which the said cyclic ether is a monoetherhaving from two to ten carbon atoms and from zero to three halogensubstituents selected from the group consisting of chloro and bromoradicals, the said aldehyde is a monomeric aldehyde of from one to 12carbon atoms and from zero to three halogen substituents selected fromthe group consisting of chloro and bromo radicals, and the saidpolymerization starter is present in an amount of from 0.2 percent to 50percent by weight of the total reactant mixture.

3. The process of claim 2 in which the said polymeric compositions havea molecular-weight distribution such that the ratio of theweight-average molecular weight to the number-average molecular weightdoes not exceed 1.5.

4. The process of claim 2 in which the copolymeric 5. The process ofclaim 4 in which the aromatic ring of said aromatic aldehyde has sixcarbon atoms.

6. The process of claim 2 in which the copolymeric composition has amolecular weight of at least 500 and the said cyclic ether is asaturated aliphatic monoepoxide having from two to six carbon atoms andsaid aldehyde is a lower aliphatic monoaldehyde having from one to sixcarbon atoms and from zero to three halogen substituents selected fromthe group consisting of chloro and bromo radicals, and said anhydride isa cyclic monoanhydride.

7. The process of claim 6 in which the said aldehyde is formaldehyde.

8. The process of claim 6 in which the said aldehyde is acetaldehyde.

9. The process of claim '6 in which the said aldehyde is chloral.

10. The process of claim 6 in which the said aldehyde is bromal.

11. The process of claim 6 in which the said aldehyde is anethylenically unsaturated lower aliphatic monoaldehyde.

12. The process of claim 6 in which the starter is water.

13. The process of claim 6 in which the starter is an inorganichydrogen-containing acid capable of effecting the ring-opening reactionof said cyclic ether and said anhydride.

14. The process of claim 13 in which the starter is selected from thegroup consisting of phosphoric acid and phosphorous acid.

15. The process of claim 6 in which the starter is an organic compoundhaving at least one radical selected from the group consisting ofhydroxyl, carboxyl, and sulfhydryl radicals.

16. The process of claim 15 in which the said monoepoxide is selectedfrom the group consisting of ethylene oxide, propylene oxide,1,2-butylene oxide, and epichlorohydrin, and the said cyclic anhydrideis selected from the group consisting of phthalic anhydride,3,4,5,6-tetrachlorophthalic anhydride, 3,4,5,6-tetrabromophthalicanhydride, 3,4,5,6-tetrahydrophthalic anhydride, maleic anhydride,itaconic anhydride, succinic anhydride, 1,4,5,6 ,7- hexachlorobicyclo(2,2,1) S-heptene-Z,3-dicarboxylic acid anhydride, diphenic anhydride,and trimellitic anhydride, and the said starter is selected from thegroup consisting of ether polyols of from 4 to 18 carbon atoms andaliphatic alcohols having from 1 to 18 carbon atoms and from 1 to 8hydroxyl groups.

17. The process of claim 15 in which the said monoepoxide is selectedfrom the group consisting of ethylene oxide, propylene oxide,1,2-butylene oxide, and epichlorohydrin, and the said cyclic anhydrideis selected from the group consisting of phthalic anhydride, 3,4,5,6-tetrachlorophthalic anhydride, 3,4,5,6-tetrabromophthalic anhydride,3,4,52,6-t6ll1fll'lYdI'OPhthElllC anhydride, 1,4,5,6,7-hexachlorobicyclo (2,2,1) S-heptene-Z,3-dicarboxylic acid anhydride,diphenic anhydride, trimellitic anhydride, maleic anhydride, itaconicanhydride, and succinic anhydride, and said starter is selected from thegroup consisting of organic carboxylic acids having from 1 to 54 carbonatoms and from one to three car-boxylic acid groups andhydroxylcarboxylic acids having from 2 to 18 carbon atoms, from 1 to 5hydroxyl groups and from one to three carboxylic acid groups.

18. The process of claim 15 in which the said monoepoxide is selectedfrom the group consitsing of ethylene oxide, propylene oxide,1,2-butylene oxide, and epichlorohydrin, and the said cyclic anhydrideis selected from the group consisting of phthalic anhydride,3,4,5,6-tetrachlorophthalic anhydride, 3,4,5,6-tetrabromophthalicanhydride, 3,4,5,6-tetrahydrphthalic anhydride, 1,4,5,6,7-hexachlorobicyclo (2,2,1) -heptene-2,3-dicarboxylic acid anhydride,diphenic anhydride, trimellitic anhydride, maleic anhydride, itaconicanhydride, and succinic anhydride, and said starter is a saccharide.

19. The process of claim 18 in which said saccharide has from five totwelve carbon atoms and from four to eight hydroxyl groups.

20. The process of claim in which said saccharide is dextrose.

21. The process of claim 6 in which the starter has from one to 24carbon atoms and 1 to 6 sulfhydryl groups.

22. The process of producing polymeric compositions having a molecularweight of at least 500 and containing in the polymer chains amultiplicity of internal ester, ether and acetal linkages, said acetallinkages being present in sequence in the form of polyacetal blocks,which comprises reacting together at a temperature of about 70 C. toabout 225 C. sufiicient for the reactants to polymerize, and at apressure at least equal to the vapor pressure of the system at thereaction temperature (1) a cyclic ether selected from the groupconsisting of epoxides and oxetanes having from 2 to ten carbon atomsand from O to 3 halogen substituents selected from the group consistingof chloro and bromo radicals, (2) an acid anhydride selected from thegroup consisting of the cyclic anhydrides and linear anhydrides oforganic polycarboxylic acids having from 4 to 14 carbon atoms, and (3) alinear polyacetal derived from a lower aliphatic aldehyde having fromone to six carbon atoms and from zero to three halogen substituentsselected from the group consisting of bromo and chloro radicals, andbeing terminated with active hydrogen-containing end groups, the ratioof reactive cyclic other groups in said cyclic ether to anhydride groupsin said polycarboxylic acid anhydride ranging from about one-to-one, toabout six-to-one, and the amount of said linear polyacetal varying fromabout one percent to 95 percent by weight of the total reactant mixture.

23. The process of claim 22 in which the said cyclic ether is asaturated, aliphatic monoepoxide having from two to six carbon atoms andsaid anhydride is a cyclic monoanhydride of an organic polycarboxylicacid having from 4 to 14 carbon atoms.

24. The process of claim 23 in which the said monoepoxide is selectedfrom the group consisting of ethylene oxide, propylene oxide,1,2-.butylene oxide, and epichlorohydrin, and the cyclic anhydride isselected from the group consisting of phthalic anhydride, maleicanhydride, itaconic anhydride, succinic anhydride, 1,4,5,6,7-hexachlorobicyclo (2,2,1) 5-heptene-2,3-dicarboxylic acid anhydride,3,4,5,6-tetrachlorophthalic anhydride, 3,4,5,6- tetrabromophthalicanhydride, 3,4,5,6 tetrahydrophthalic anhydride, diphenic anhydride, andtrimellitic anhydride.

25. The process of claim 24 in which the linear polyacetal ispolyoxymethylene.

26. The process of claim 24 in which the linear polyacetal ispolyacetaldehyde.

27. The process of claim 24 in which the linear polyacetal ispolychloral.

28. The process of claim 24 in which the linear polyof ester, ether,acetal and amide linkages to a residue derived from a polymerizationstarter selected from the group consisting of water, ammonia,hydrogen-containing inorganic acids capable of effecting thering-opening reaction of cyclic ethers and anhydrides, and organic com-24 pounds having at least one radical selected from the group consistingof hydroxyl, carboxyl, sulfhydryl, and amino radicals, and mixturesthereof, the said polymer chains being essentially composed of amultiplicity of (Y) OC-RC, and (Z) O-CH it it units wherein -OR- is anoxyalkylene radical selected from the group consisting of1,3-oxyalkylene radicals and 1,4-oxyalkylene radicals and R is analkylene radical selected from the group consisting of 1,2-alkyleneradicals and 1,3-alkylene radicals of from two to twenty carbon atomsand from 0 to 3 halogen substituents selected from the group consistingof chloro and bromo radicals, R is a hydrocarbon radical of from two totwelve carbon atoms and from zero to six halogen substituents selectedfrom the group consisting of chloro and bromo radicals, and R isselected from the group consisting of hydrogen and hydrocarbon radicalshaving from one to twelve carbon atoms and from zero to three halogensubstituents selected from the group consisting of chloro and bromoradicals, said units being joined through ester, ether, and acetallinkages in a structural arrangement in which the said X and Z unitsoccur in the polymer chains both individually and in multiple adjacentsequences to form runs, and said Y units occur individually separated byX and Z units, with the said starter residues amounting to from about0.1 percent to about 50 percent by weight of the copolymer, the Z unitsamounting to about 5 to 75 percent by weight of the copolymer, and withthe ratio of R to R ranging from about 1.5 up to about 10.

30. The composition of claim 29 having a molecular weight of at least500.

31. The composition of claim 29 having a molecular weight distributionsuch that the ratio of weight-average molecular weight to thenumber-average molecular weight is less than 1.5.

32. The composition of claim 30 in which R is a saturated aliphatic1,2-alkylene radical of from two to ten carbon atoms and from zero tothree halogen substituents selected from the group consisting of chloroand bromo radicals, and R" is an aryl radical.

33. The composition of claim 32 in which R" is a monocyclic aryl radicalhaving six carbon atoms in the aryl ring.

34. The composition of claim 30 in which R is a saturated aliphatic1,2-alkylene radical of from two to ten carbon atoms and from zero tothree halogen substituents selected from the group consisting of chloroand bromo radicals and R" is selected from the group consisting ofhydrogen and lower aliphatic radicals having from one to six carbonatoms and from zero to three halogen substituents selected from thegroup consisting of chloro and bromo radicals 35. The composition ofclaim 34 in which R" is hydrogen.

36. The composition of claim 34 in which R" is methyl.

37. The composition of claim 34 in which R" is trichloromethyl.

38. The composition of claim 34 in which R" is tribromomethyl.

89. The composition of claim 34 in which R" is an ethylenicallyunsaturated lower aliphatic hydrocarbon radical.

40. The composition of claim 34 in which the polymerization starterresidue is selected from the group consisting of -O, N, and anionicresidues of hydrogen-containing inorganic acids.

41. The composition of claim 34 in which the polymerization starterresidue is derived from an organic compound having at least one radicalselected from the group consisting of hydroxyl, carboxyl, sulfhydryl,and amino radicals.

42. The composition of claim 41 in which the said =1,2-

alkylene radical is selected from the group consisting of 1,2-ethylene,1,2-propylene, 1,2-butylene, and 3-chl0ro- 1,2-propylene, and R isselected from the group consisting of 1,2-phenylene,3,4,5,6-tetrachloro-1,2-phenylene, 3,4,5,6 tetrabromo-1,2-phenylene,3,4,5,6-tetrahydro-1,2- phenylene, 1,-2-ethenylene,l-rnethylene-1,2-ethylene, 1,2- ethylene, hex-achlorobicycloheptenylene,2,2'-diphenylene, and 4-carboxy-l,2-phenylene, and the said starter isselected from the group consisting of ether polyols of from 4 to 18carbon atoms and aliphatic alcohols having from 1 to 18 carbon atoms andfrom 1 to 8 hydroxyl groups.

43. The composition of claim 41 in which the said 1,2- alkylene radicalis selected from the group consisting of 1,2-ethylene, 1,2-propylene,1,2-butylene, and 3-chloro- 1,2-propylene, and R is selected from thegroup consisting of 1,2-phenylene, 3,4,5,6-tetrachloro-1,2-phenylene,3,4,S,6-tetrabromo-1,2-phenylene, 3,4,5,6-tetrahydro- 1,2-phenylene,1,2-ethenylene, l-methylene-1,2-ethylene, 1,2-ethylene,hexachlorobicycloheptenylene, 2,2-diphenylene, and4-carboxy-1,2-phenylene, and the said starter is selected from the groupconsisting of organic carboxylic acids having from 1 to 54 carbon atomsand from one to three carboXylic acid groups and hydroxyl carboxylicacids having from 2 to 18 carbon atoms, from 1 to 5 hydroxyl groups andfrom one to three carboxylic acid groups.

44. The composition of claim 41 in which the said 1,2-alkylene radicalis selected from the group consisting of 1,2-ethylene, 1,2-propylene,1,2-butylene, and 3-chloro- 1,2-propylene, and R is selected from thegroup consisting of 1,2-pheny1ene, 3,4,5,6-tetrachl0r0-1,2-phcnylene,3,4,5,6 tetrabrom-o-1,2-phenylene, 3,4,5,6-tetrahydro-l,2- phenylene,1,2-ethenylene, l-methylene-l,Z-ethylene, 1,2- ethylene,hexachlorobicycloheptenylene, 2,2'-diphenylene, and4-carboXy-l,2-phenylene, and the said starter is a saccharide.

45. The composition of claim 41 in which the said 1,2- alkylene radicalis selected from the group consisting of 1,2-ethylene, 1,2-propylene,1,2-butylene, and 3-chloro- 1,2-propylene, and R is selected from thegroup consisting of 1,2-phenylene, 3,4,5, 6-tetrachloro-1,-2-phenylene,3,4,5,6 -tetrabromo-1,2-phenylene, 3,4,5,6-tetrahydro- 1,2-phenylene,1,2-ethenylene, l-methylene-1,2-ethylene, 1,2-ethylene,hexachlorobicycloheptenylene, 2,2-diphenylene, and4-carboXy-1,2-phenylene, and the said starter has from one to 24 carbonatoms and from 1 to 6 sulfhydryl groups.

46. A thermoplastic fusible ternary block copolymer having end groupsselected from the group consisting of OH and COOH radicals and havingthe formula EABA-E where E is the terminal radical, A is apolyester-ether binary copolymer block of the formula with R being analkylene radical selected from the group consisting of 1,2 -alkyleneradicals and 1,3-alkylene radicals having from two to twenty carbonatoms and from zero to three halogen substituents selected from thegroup consisting of chloro and bromo radicals, R is a hydrocarbonradical of from two to twelve carbon atoms and from zero to six halogensubstituents selected from the group consisting of chloro and bromoradicals, n is a positive whole number varying from one to about fifteenwith the average value of n varying from about 1.5 up to about ten, andq is a positive whole number varying from one to fifty, and B is apolyacetal block of the structure O-OH t with R" being selected from thegroup consisting of hydrogen and hydrocarbon radicals having from one totwenty carbon atoms and from zero to three halogen substituents selectedfrom the group consisting of chloro and bromo radicals and m is apositive whole number varying from five to 500, said A blocksconstituting from about 5 to about percent by weight of the ternarycopolymer, said ternary copolymer having a molecular weight of at least500.

47. The composition of claim 46 wherein R is a 1,2- alkylene radical offrom two to six carbon atoms and from zero to three halo-gensubstituents selected from the group consisting of chloro and bromoradicals.

48. The composition of claim 47 wherein R is selected from the groupconsisting of 1,2-ethylene, 1,2-propylene, and 1,2-butylene and R isselected from the group consisting of 1,2-ethylene, 1,2-ethenylene,l-methyl-1,2-ethylene, 1,2 phenylene,3,4,5,6-tetrachlo-ro-1,Z-phenylene, 3,4,5, 6 tetrabromo-1,2-phenylene,3,4,5,6-tetrahydro-1,2- phenylene, 1,2 ethylene,heXachlorobicycloheptenylene, and 2,2-diphenylene.

49. The composition drogen.

50. The composition of claim 48 in which R is lower alkyl.

51. The composition of claim 48 in which R" is trichloro-methyl.

52. The composition of claim 43 in which R" is tribr-omomethyl.

53. A thermoset, infusible random ternary copolymer consistingessentially of polymer chains carrying at one chain end terminal groupsselected from the group consisting of hydroxyl and carboxylic acidradicals and being joined at the other chain end through linkagesselected from the group consisting of ester, ether, acetal and amidelinkages to a residue derived from a polymerization starter selectedfrom the group consisting of water, ammonia, inorganic acids capable ofeffecting the ringopening reaction of cyclic ethers and anhydrides, andorganic compounds having at least one radical selected from the groupconsisting of hydroxyl, carboxyl, sulfhydryl, and amino radicals, andmixtures thereof, the said polymer chains being essentially composed ofa multiplicity of'(X) -O-R,

I RI! units wherein O-R- is an oxyalkylene radical selected from thegroup consisting of 1,3-oxyalkylene radicals and 1,4-oxyalkyleneradicals and R is an alkylene radical selected from the group consistingof 1,2-alkylene radicals and 1,3-alkylene radicals of from two to twentycarbon atoms and from 0 to 3 halogen substituents selected from thegroup consisting of chloro and bromo radicals, R is a hydrocarbonradical of from two to twelve carbon atoms and from zero to six halogensubstituents selected from the group consisting of chloro and bromoradicals, and R" is selected from the group consisting of hydrogen andhydrocarbon radicals having from one to twelve carbon atoms and fromzero to three halogen substituents selected from the group consisting ofchloro and bromo radicals, said units being joined through ester, ether,and acetal linkages in a structural arrangement in which the said X andZ units occur in the polymer chains both individually and in multipleadjacent sequences to form runs, and said Y units occur individuallyseparated by X and Z units, with the said starter residues amounting tofrom about 0.1 percent to about 50 percent by weight of the copolymer,the Z units amounting to about 5 to 75 percent by weight of thecopolymer, and with the ratio of -R to R ranging from about 1.5 up toabout 10!, and with the said polymer chains being cross-linked throughpolyfunctional units having a functionality of at least 4 and beingselected from the said X, Y, and Z units, with the weight fraction ofthe said polyfunctional units amounting to at least about 2 percent byweight of the total composition.

54. A thermoset, infusible ternary copolymer having of claim 48 in whichR" is hyend groups selected from the group consisting of OH and COOHradicals and having chains of the formula where E is the terminalradical, A is a polyester-ether binary copolyrner block of the formula{(oR)no-(lJ-R'?} (l (l with R being an alkylene radical selected fromthe group consisting of 1,2-alkylene radicals and 1,3-a1kylene radicalshaving from two to twenty carbon atoms and from zero to three halogensubstituents selected from the group consisting of chloro and brornoradicals, R is a hydrocarbon radical of from two to twelve carbon atomsand from zero to six halogen substituents selected from the .groupconsisting of chloro and bromo radicals, n is a positive whole numbervarying from one to about fifteen with the average value of n varyingfrom about 1.5 up to about ten, and q is a positive whole number varyingfrom one to fifty, and B is a polyacetal block of the structure with R"being selected from the group consisting of hydrogen and hydrocarbonradicals having from one to twenty carbon atoms and from zero to threehalogen substituents selected from the group consisting of chloro andbrorno radicals and m is a positive whole number varying from five to500, said A blocks constituting from about to about 95 percent by weightof the ternary copolyrner, and with the said polymer chains beingcrosslinked through polyfunction al units having a functionality of atleast 4 and being selected from the said R and R radicals, with theweight fraction of the said polyfunctional units amounting to at leastabout 2 percent by weight of the total composition.

55. The process of producing ternary copolymeric compositions containinga multiplicity of ester, other and acctal units in substantially randomdistribution in the polymer chains, which comprises reacting together ina closed system at a temperature of about 70 C. to 225 C. (1) a cyclicether selected from the group consisting of epoxides and oxetanes, (2) acyclic anhydride of an organic polycarboxylic acid having from four tofourteen carbon atoms and from zero to six halogen substituents selectedfrom the group consisting of chloro and brorno radicals, (3) analdehyde, and (4) from 0 to 50 percent by weight of the total reactantmixture of a polymerization starter selected from the group consistingof water, ammonia, hydrogen-containing inorganic acids capable ofeffecting the ring-opening reaction of said (1) and (2), and organiccompounds having at least one radical selected from the group consistingof hydroxyl, carboxyl, sulfhydryl, and amino radicals, and mixturesthereof, the ratio of mols of reactive cyclic ether groups in saidcyclic ether to mols of anhydride groups in said polycarboxylic acidanhydride ranging from one-toone to about ten-to-one, and the amount ofaldehyde varying from about one percent to about 99 percent by weight ofthe total reactant mixture.

56. The process of claim in which the said cyclic ether is a monoetherhaving from two to ten carbon atoms and from zero to three substituentsselected from the group consisting of chloro and brorno radicals, thesaid aldehyde is a monomeric aldehyde of from one to 12 carbon atoms andfrom zero to three halogen substituents selected from the groupconsisting of chloro and romo radicals, and the said polymerizationstarter is present in an amount of from 0.2 percent to 50 percent byweight of the total reactant mixture.

57. A polyurethane composition comprising the reaction product of (1) anorganic polyisocyanate and (2) a hydroxyl-terminated thermoplasticterpolymer selected from the group consisting of the hydroxyl-terminatedcompositions of claim 32.

58. A polyurethane composition comprising the reaction product of (1) anorganic polyisocyanate and (2) a hydroxyl-terrninated thermoplasticterpolymer selected from the group consisting of the hydroxyl-terminatcdcompositions of claim 34.

59. A polyurethane composition comprising the reaction product of (1) anorganic polyisocyanate and (2) a hydroXyl-terminated thermoplasticterpolymer selected from the group consisting of the hydroxyl-terminatedcompositions of claim 46.

60. A cross-linked composition comprising the reaction product of (1) afree-radically reactive vinyl monomer and (2) a free-radically reactiveunsaturated thermoplastic terpolymer selected from the group consistingof the free-radically reactive unsaturated thermoplastic compositions ofclaim 32.

61. A crosslinked composition comprising the reaction product of (11) afree-radically reactive vinyl monomer and (2) a free-radically reactiveunsaturated thermoplastic terpolymer selected from the group consistingof the free-radically reactive unsaturated thermoplastic compositions ofclaim 34.

62. A cross-linked composition comprising the reaction product of (1) afree-radically reactive vinyl monomer and (2) a free-radically reactiveunsaturated thermoplastic terpolymer selected from the group consistingof the free-radically reactive unsaturated thermoplastic compositions ofclaim 46.

References Cited UNITED STATES PATENTS 3,326,857 6/ 1967 Kawasumi et a1.26067 3,000,860 9/1961 Brown et al. 26067 3,046,249 7/1962 Hermann etal. 26067 3,213,067 10/1965 Phol et al 26078.4 3,219,630 11/1965 Sidi26067 3,254,060 5/1966 Connolly et al. 26078.4 3,293,218 12/1966 Sidi26067 3,293,222 12/1966 Sidi 26067 DONALD E. CZAJA, Primary Examiner.

R. W. GRIFFIN, Assistant Examiner.

